10-(dibutylboryl)-1-(4-iodobenzoyl)-5-mesityldipyrromethane | 816454-79-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 10-(dibutylboryl)-1-(4-iodobenzoyl)-5-mesityldipyrromethane
• 英文别名: [1-dibutylboranyl-5-[1H-pyrrol-2-yl-(2,4,6-trimethylphenyl)methyl]pyrrol-2-yl]-(4-iodophenyl)methanone
• CAS: 816454-79-2
• 化学式: C₃₃H₄₀BIN₂O
• 分子量: 618.409
• InChiKey: ZHYWCUPBKFDPBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  37.8
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  10-(dibutylboryl)-1-(4-iodobenzoyl)-5-mesityldipyrromethane 在 sodium tetrahydroborate 、 乙基溴化镁 、 六甲基二硅氮烷 、 ytterbium(III) triflate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 4.09h， 生成
  参考文献：
  名称：

  Meso-¹³C-Labeled Porphyrins for Studies of Ground-State Hole Transfer in Multiporphyrin Arrays

  摘要：

  Understanding electronic communication among interacting chromophores provides the foundation for a variety of applications. The ground-state electronic communication in diphenylethyne-linked zinc-porphyrin dyads has been investigated by a novel molecular design strategy that entails introduction of a C-13-atom (*) at specific sites of the porphyrins where there is substantial electron density in the relevant frontier (highest occupied) molecular orbital. The site of C-13 substitution is at a meso-position, either the site of attachment of the linker (proximal, "P") or the site trans to the linker (distal, "D"). The substituents (R) at the non-linking meso-positions are mesityl, tridec-7-yl ("swallowtail"), or p-tolyl groups. Altogether five isotopically labeled porphyrin dyads have been prepared. The hole/electron-transfer properties of one-electron oxidized dyads have been examined by electron paramagnetic resonance (EPR) spectroscopy. The introduction of the meso-C-13 label provides a "clock" (via the hyperfine interactions) that allows investigation of a time scale for hole transfer that is 3-4 times shorter than that provided by the natural abundance N-14 nuclei of the pyrrole nitrogen atoms. The EPR studies indicate that the hole transfer, which has been previously shown to be fast on the time scale of the N-14 hyperfine clock (similar to 220 ns), remains fast on the time scale of the C-13 hyperfine clock (similar to 50 ns).

  DOI：

  10.1021/jo070593x
• 作为产物：
  描述：

  2-(二吡咯-2-基)甲基三甲苯 在 TEA 、 乙基溴化镁 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 10-(dibutylboryl)-1-(4-iodobenzoyl)-5-mesityldipyrromethane
  参考文献：
  名称：

  Meso-¹³C-Labeled Porphyrins for Studies of Ground-State Hole Transfer in Multiporphyrin Arrays

  摘要：

  Understanding electronic communication among interacting chromophores provides the foundation for a variety of applications. The ground-state electronic communication in diphenylethyne-linked zinc-porphyrin dyads has been investigated by a novel molecular design strategy that entails introduction of a C-13-atom (*) at specific sites of the porphyrins where there is substantial electron density in the relevant frontier (highest occupied) molecular orbital. The site of C-13 substitution is at a meso-position, either the site of attachment of the linker (proximal, "P") or the site trans to the linker (distal, "D"). The substituents (R) at the non-linking meso-positions are mesityl, tridec-7-yl ("swallowtail"), or p-tolyl groups. Altogether five isotopically labeled porphyrin dyads have been prepared. The hole/electron-transfer properties of one-electron oxidized dyads have been examined by electron paramagnetic resonance (EPR) spectroscopy. The introduction of the meso-C-13 label provides a "clock" (via the hyperfine interactions) that allows investigation of a time scale for hole transfer that is 3-4 times shorter than that provided by the natural abundance N-14 nuclei of the pyrrole nitrogen atoms. The EPR studies indicate that the hole transfer, which has been previously shown to be fast on the time scale of the N-14 hyperfine clock (similar to 220 ns), remains fast on the time scale of the C-13 hyperfine clock (similar to 50 ns).

  DOI：

  10.1021/jo070593x

文献信息

• Probing Ground-state Hole Transfer Between Equivalent, Electrochemically Inaccessible States in Multiporphyrin Arrays Using Time-resolved Optical Spectroscopy
  作者：Hee-eun Song、Masahiko Taniguchi、Christine Kirmaier、David F. Bocian、Jonathan S. Lindsey、Dewey Holten

  DOI：10.1111/j.1751-1097.2008.00471.x

  日期：2009.5

  selectively oxidized to produce Zn+FbFb, the free base porphyrins are excited to produce the excited‐state mixture Zn+Fb*Fb and Zn+FbFb*, and the subsequent dynamics are monitored by ultrafast absorption spectroscopy. The system evolves by a combination of energy‐ and hole‐transfer processes involving (adjacent and nonadjacent) zinc and free base porphyrin constituents that are complete within 100 ps of excitation;

  描述并实施了一种新策略，用于确定多卟啉结构中等效卟啉之间的空穴转移率。该方法允许在不是阵列中最容易氧化的组分的位点之间访问这些速率。使用这种新策略研究的特定结构是由一个锌卟啉 (Zn) 和两个游离碱卟啉 (Fb) 组成的三联体。三联体使用二苯乙炔接头 (ZnFbFbU) 和亚苯基接头 (ZnFbFbΦ)。锌卟啉被选择性氧化生成 Zn+FbFb，游离碱卟啉被激发生成激发态混合物 Zn+Fb*Fb 和 Zn+FbFb*，随后的动力学由超快吸收光谱监测。该系统通过能量和空穴转移过程的组合发展，涉及（相邻和非相邻）锌和游离碱卟啉成分，在 100 ps 激发内完成；许多这些过程的速率常数来自先前对基准二元组（ZnFbU 和 ZnFbΦ）氧化形式的研究。激发态衰变通道之一产生亚稳态 ZnFbFb+，通过目标空穴转移过程衰变为第二个亚稳态 ZnFb+Fb，然后快速空穴转移以产生系统的 Zn+FbFb 热力学基态。发现氧化的
• Boron-Complexation Strategy for Use with 1-Acyldipyrromethanes
  作者：Kannan Muthukumaran、Marcin Ptaszek、Bruce Noll、W. Robert Scheidt、Jonathan S. Lindsey

  DOI：10.1021/jo0492620

  日期：2004.8.1

  1-Acyldipyrromethanes are important precursors in rational syntheses of diverse porphyrinic compounds. 1-Acyldipyrromethanes are difficult to purify, typically streaking upon chromatography and giving amorphous powders upon attempted crystallization. A solution to this problem has been achieved by reacting the 1-acyldipyrromethane with a dialkylboron triflate (e.g., Bu2B-OTf or 9-BBN-OTf) to give the corresponding B,B-dialkyl-B-(1-acyldipyrromethane)boron(III) complex. The reaction is selective for a 1-acyldipyrromethane in the presence of a dipyrromethane. The 1-acyldipyrromethane-boron complexes are stable to routine handling, are soluble in common organic solvents, are hydrophobic, crystallize readily, and chromatograph without streaking. The 1-acyldipyrromethane can be liberated in high yield from the boron complex upon treatment with 1-pentanol. Alternatively, the 1-acyldipyrromethane-boron complex can be used in the formation of a trans-A(2)B(2)-porphyrin. In summary, the boron-complexation strategy has broad scope and greatly facilitates the isolation of 1-acyldipyrromethanes.
• 9-Acylation of 1-Acyldipyrromethanes Containing a Dialkylboron Mask for the α-Acylpyrrole Motif
  作者：Syeda Huma H. Zaidi、Kannan Muthukumaran、Shun-ichi Tamaru、Jonathan S. Lindsey

  DOI：10.1021/jo048587d

  日期：2004.11.1

  1,9-Diacyldipyrromethanes are important precursors to porphyrins, yet synthetic access remains limited owing to (1) poor conversion in the 9-acylation of 1-acyldipyrromethanes and (2) handling difficulties because acy1dipyrromethanes typically streak upon chromatography and give amorphous powders upon attempted crystallization. A reliable means for converting a dipyrromethane to a 1-acyldipyrromethane-dialkylboron complex was recently developed, where the dialkylboron (BR2) unit renders the complex hydrophobic and thereby facilitates isolation. Herein a refined preparation of 1,9-diacyldipyrromethanes is presented that employs the 1-acyldipyrromethane-BR2 complex as a substrate for 9-acylation. The dialkylboron unit provides protection for the alpha-acylpyrrole unit. 9-Acylation requires formation of the pyrrolyl-MgBr reagent and the presence of 1 equiv of a nonnucleophilic base to quench the proton liberated upon alpha-acylation. Reaction of the 1-acyldipyrromethane-BR2 complex (1 equiv) with mesitylmagnesium. bromide (2 equiv) followed by the addition of an acylating agent (S-2-pyridyl thioate or acid chloride, 1.1 equiv) gives the corresponding 1,9-diacyldipyrromethane-BR2 complex. The acylation method afforded 1,9-diacyldipyrromethaneBR(2) complexes with limited or no chromatography in yields of 64-92%. The 1,9-diacyldipyrromethane-BR2 complexes are stable to routine handling, are readily soluble in common organic solvents, crystallize readily, and can now be prepared in multigram quantities through use of stoichiometric quantities of reagents.